Method of producing epitaxial silicon wafer, epitaxial silicon wafer, and method of producing solid-state image sensing device

ABSTRACT

Provided is an epitaxial silicon wafer with reduced metal contamination achieved by higher gettering capability and a method of efficiently producing the same. 
     The method of producing an epitaxial wafer includes a wafer production step of pulling a single crystal silicon ingot having a COP formation region by Czochralski process, and subjecting the obtained single crystal silicon ingot to slicing, thereby producing a silicon wafer  10  including COPs; a cluster ion irradiation step of irradiating the produced silicon wafer  10  with cluster ions  16  to form a modifying layer  18  formed from a constituent element of the cluster ions  16 , contained as a solid solution in a surface portion  10 A of the silicon wafer  10 ; and an epitaxial layer formation step of forming an epitaxial layer  20  on the modifying layer  18  of the silicon wafer  10.

CROSS-REFERENCE TO RELATED

This application is a division of application Ser. No. 14/078,286, filedNov. 12, 2013, which is expressly incorporated herein by reference inits entirety.

BACKGROUND

Metal contamination is a major cause of deterioration in characteristicsof a semiconductor device. For example, for a back-illuminatedsolid-state image sensing device, metal mixed into a semiconductorepitaxial wafer to be a substrate of the device causes increased darkcurrent in the solid-state image sensing device, and results information of defects referred to as white spot defects. Recently, aback-illuminated image sensing device has been widely used for digitalcameras and mobile phones such as smartphones because it can directlyreceive light from the outside, and take sharper images or motionpictures even in a dark place and the like due to the fact that a wiringlayer and the like thereof are disposed at a lower layer than a sensorunit. Therefore, it is desirable to reduce white spot defects as much aspossible.

Mixing of metal into a wafer mainly occurs in a process of producing asemiconductor epitaxial wafer and a process of producing a solid-stateimage sensing device (device fabrication process). Metal contaminationin the former process of producing a semiconductor epitaxial wafer maybe due to heavy metal particles from components of an epitaxial growthfurnace, or heavy metal particles caused by metal corrosion of pipingmaterials of the furnace due to chlorine-based gas used in epitaxialgrowth in the furnace. In recent years, such metal contaminations havebeen reduced to some extent by replacing components of epitaxial growthfurnaces with highly corrosion resistant materials, but not to asufficient extent. On the other hand, in the latter process of producinga solid-state image sensing device, heavy metal contamination ofsemiconductor substrates would occur in process steps such as ionimplantation, diffusion, and oxidizing heat treatment in the producingprocess.

For these reasons, conventionally, heavy metal contamination ofsemiconductor epitaxial wafers has been avoided by forming, in thesemiconductor wafer, a gettering sink for trapping the metal, or using asubstrate, such as a high boron concentration substrate, having highability to trap the metal (gettering capability).

In general, a gettering sink is formed in a semiconductor wafer by anintrinsic gettering (IG) method in which oxygen precipitate s (commonlycalled a silicon oxide precipitate, and also called BMD: bulk microdefect) or dislocations that are crystal defects are formed within thesemiconductor wafer, or an extrinsic gettering (EG) method in which thegettering sink is formed on the rear surface of the semiconductor wafer.

Here, a technique of forming gettering sites in a semiconductor wafer byion implantation can be given as a technique for gettering heavy metal.JP 06-338507 A (PTL 1) discloses a producing method, by which carbonions are implanted through a surface of a silicon wafer to form a carbonion implanted region, and a silicon epitaxial layer is formed on itssurface thereby obtaining an epitaxial silicon wafer. In that technique,the carbon ion implanted region functions as gettering sites.

Further, JP 2008-294245 A (PTL 2) discloses a method of forming a carbonimplanted layer by implanting carbon ions into a silicon wafer, and thenperforming heat treatment using a rapid thermal annealing (RTA)apparatus for recovering the crystallinity of the wafer which has beendisrupted by the ion implantation, thereby shortening the recovery heattreatment process.

Further, JP 2010-177233 A (PTL 3) discloses a method of producing anepitaxial wafer, comprising the steps of ion-implanting at least one ofboron, carbon, aluminum, arsenic, and antimony at a dose in the range of5×10¹⁴ atoms/cm² to 1×10¹⁶ atoms/cm² into a single crystal silicon ingotsubstrate; then cleaning the single crystal silicon ingot substratesubjected to the ion implantation, without recovery heat treatment; andthen forming an epitaxial layer at a temperature of 1100° C. or moreusing a single wafer processing epitaxial apparatus.

CITATION LIST Patent Literature

PTL 1: JP 06-338507 A

PTL 2: JP 2008-294245 A

PTL 3: JP 2010-177233 A

SUMMARY

This summary is provided to introduce a selection of concepts in asimplified form that are further described below in the DetailedDescription. This summary is not intended to identify key features ofthe claimed subject matter, nor is it intended to be used as an aid indetermining the scope of the claimed subject matter.

The present invention relates to a method of producing an epitaxialsilicon wafer, an epitaxial silicon wafer, and a method of producing asolid-state image sensing device. The present invention relates inparticular to a method of efficiently producing an epitaxial siliconwafer, which can achieve higher gettering capability thereby suppressingmetal contamination.

DESCRIPTION OF THE DRAWINGS

The foregoing aspects and many of the attendant advantages of thisinvention will become more readily appreciated as the same become betterunderstood by reference to the following detailed description, whentaken in conjunction with the accompanying drawings, wherein:

FIGS. 1A to 1D are schematic cross-sectional views illustrating a methodof producing an epitaxial silicon wafer 100 of the present invention.

FIG. 2 is a diagram showing the relationship between the ratio of thepulling speed to the temperature gradient at the solid-liquid interfaceand crystalline regions forming a single crystal silicon ingot.

FIG. 3 is a diagram schematically showing pulling of a single crystalsilicon ingot.

FIG. 4A is a schematic view illustrating an irradiation mechanism of theirradiation with cluster ions, and FIG. 4B is a schematic viewillustrating an implantation mechanism of the implantation of monomerions.

FIGS. 5A and 5B are diagrams showing single crystal pulling apparatusesused in Examples.

FIG. 6 is a graph showing profiles of carbon concentration with respectto the depth from the surface of a silicon wafer between InventionExample 1 and Comparative Example 1.

FIGS. 7A and 7B are graphs for comparing the capability of Cu getteringin Invention Example 1 and Comparative Example 1.

FIG. 8 is a graph showing the relationship between the residence time inCOP formation temperature range and the maximum size of COPs.

FIG. 9 shows a graph showing the relationship between the COP size andthe COP density.

DETAILED DESCRIPTION

Embodiments of the present invention will be described below in detailwith reference to the drawings. In principle, the same components aredenoted by the same reference numeral, and the description will not berepeated. In FIG. 1C, an epitaxial layer 20 is exaggerated with respectto a silicon wafer 10 in thickness for the sake of explanation, so thethickness ratio does not conform to the actual ratio.

As shown in FIGS. 1A to 1C, a method of producing an epitaxial siliconwafer 100 according to the present invention includes a wafer productionstep of pulling a single crystal silicon ingot (not shown) having a COPformation region by Czochralski process (CZ method), and subjecting theobtained single crystal silicon ingot (not shown) to slicing, therebyproducing a silicon wafer 10 including COPs (FIG. 1A); a cluster ionirradiation step of irradiating the produced silicon wafer 10 withcluster ions 16 to form a modifying layer 18 formed from a constituentelement of the cluster ions 16 in a surface portion 10A of the siliconwafer 10; and an epitaxial layer formation step of forming an epitaxiallayer 20 on the modifying layer 18 of the silicon wafer 10. FIG. 1D is aschematic cross-sectional view of the epitaxial silicon wafer 100obtained by the production method.

First, a silicon wafer 10 including COPs is used as a substrate of theepitaxial silicon wafer 100 in the present invention. A CZ process isemployed as a method of producing a single crystal silicon ingot that isa material of the silicon wafer 10. In producing a single crystalsilicon ingot using the Czochralski process, a single crystallinesilicon melt is supplied into a quartz crucible, the seed crystal ispulled upward while rotating the quartz crucible and the seed crystal,and thus a single crystal silicon ingot is grown downward from the seedcrystal.

It is known that various types of grown-in defects occur in thus grownsingle crystal silicon ingots, which defects affect the devicefabrication process. Typical examples of the grown-in defects includedislocation clusters that are formed in a region where interstitialsilicon is predominant due to the growth under the condition of lowpulling speed (hereinafter also referred to as “I region”) and COPs thatare formed in a region where vacancies are predominant due to the growthunder the condition of high pulling speed (hereinafter referred to as “Vregion”). Further, in the vicinity of the interface between the I regionand the V region, defects are formed in a ring shape, which defects arecalled oxidation induced stacking faults (OSF).

The distribution of these defects in a grown single crystal siliconingot is known to depend on two factors, that is, the crystal pullingspeed V and the temperature gradient G at the solid-liquid interface.FIG. 2 is a diagram showing the relationship between the ratio of thepulling speed V to the temperature gradient G at the solid-liquidinterface (V/G) and crystalline regions forming a single crystal siliconingot. As shown in the diagram, in the single crystal silicon ingot, aCOP formation region 41 which is a crystalline region where COPs aredetected is predominant when the V/G is high, whereas an OSF latentnucleus region 42 which appears as a ring-shaped OSF region whenperforming a certain oxidation heat treatment is formed when the V/G islow. COPs are not detected in this OSF region 42. Further, the siliconwafer collected from the single crystal silicon ingot grown under acondition of high pulling speed, the COP formation region 41 mostlyoccupies the wafer, so that COPs are formed in almost the entire area inthe crystal diameter direction.

With the V/G being lowered, an oxygen precipitation promoted region(hereinafter also referred to as “Pv region”) 43, which is a crystallineregion where oxygen is present and COPs are not detected is formed; anoxygen precipitation inhibited region (hereinafter also referred to as“Pi region”) 44, which is a crystalline region where oxygen is unlikelyto precipitate and COPs are not detected is then formed; and a region45, which is a crystalline region where dislocation clusters aredetected, is formed.

For a silicon wafer collected from a single crystal silicon ingot havingsuch a distribution of defects depending on the V/G, the crystallineregion other than the COP formation region 41 and the dislocationcluster region 45 is a crystalline region generally regarded as adenuded zone having no defects. The silicon wafer collected from asingle crystal silicon ingot including these crystalline regions is asilicon wafer free of dislocation clusters and COPs.

However, growth of a single crystal silicon ingot having the denudedzone is necessarily performed at a lowered ingot pulling speed V, whichresults in reduced productivity. This being the case, in the presentinvention, a single crystal silicon ingot having not the denuded zonebut the COP formation region 41 is grown, and a silicon wafer includingCOPs, which is obtained from this ingot, is used as a substrate of theepitaxial silicon wafer 100. In this specification, a “silicon waferincluding COPs” means a silicon wafer obtained from a single crystalsilicon ingot having the COP formation region 41. In growing a singlecrystal silicon ingot to be a material of a silicon ingot includingCOPs, the pulling speed V can be high, which leads to improvedproductivity and reduced cost.

Note that during the growth of a single crystal silicon ingot having theCOP formation region 41, the size and density of the COPs formed in theCOP formation region 41 vary due to thermal history of the growingingot. Here, if the size of COPs is too large, when the epitaxial layer20 is formed on the silicon wafer 10 obtained from the growing ingot,epitaxial defects caused by COPs, COP marks, and the like would beformed in the epitaxial layer 20.

The inventor of the present invention studied the conditions forsuppressing the formation of epitaxial defects to find that theformation of epitaxial defects can be effectively suppressed by pullingthe single crystal silicon ingot under growth conditions satisfying theresidence time of a single crystal silicon ingot of 150 min or less in atemperature range of 1200° C. to 1000° C. FIG. 3 is a diagramschematically showing pulling of a single crystal silicon ingot. Thetemperature range of 1200° C. to 1000° C. is a temperature range whereCOPs are formed, and shorter the residence time of the single crystalsilicon ingot I in the temperature range of 1200° C. to 1000° C.(hereinafter also referred to as “COP formation temperature range”),smaller the size of the COPs is. The inventor found that when theresidence time of the ingot I in the above temperature range is 150 orless, the maximum size of the COPs formed in the ingot I is 0.25 μm, andformation of epitaxial defects can be suppressed.

The residence time of the ingot I in the above temperature range can beadjusted by controlling the pulling speed in pulling the growing ingot Iupward. Since the distribution of crystalline regions formed in theingot I (defect distribution) varies depending on the ambienttemperature in a furnace of a single crystal pulling apparatus used, thepulling speed may be set to a range where the COP formation region canbe obtained.

Further, the residence time of the single crystal silicon ingot I in theabove COP formation temperature range can be reduced further byincreasing the rate of cooling the ingot I. The increase in the coolingrate can be realized specifically by pulling the single crystal siliconingot I while forcibly cooling around the ingot I. Here, the ingot I canbe cooled by placing a cooling member such as a water-cooling member tosurround the ingot I. Thus, the residence time of the ingot I in theabove temperature range can be shortened more, thereby further improvingthe productivity.

The polarity of the thus prepared silicon wafer 10 may be n-type orp-type. In addition to the irradiation with cluster ions describedbelow, a silicon wafer having a crystal into which carbon and/ornitrogen are added may be used to further increase gettering capability.

Next, the technical meaning of employing the step of cluster ionirradiation, which is a characteristic step of the present invention,will be described with its operation and effect. The modifying layer 18formed as a result of irradiation with the cluster ions 16 is a regionwhere the constituent element of the cluster ions 16 is localized atcrystal interstitial positions or substitution positions in the crystallattice of the surface portion 10A of the silicon wafer 10, which regionfunctions as a gettering site. The reason may be as follows. Afterirradiation in the form of cluster ions, elements such as carbon andboron are localized at high density at substitution positions andinterstitial positions in the single crystal silicon. It has beenexperimentally found that when carbon or boron is turned into a solidsolution to the equilibrium concentration of single crystal silicon orhigher, the solid solubility of heavy metals (saturation solubility oftransition metal) extremely increases. It is considered that carbon orboron made into a solid solution to the equilibrium concentration orhigher increases the solubility of heavy metals, which results insignificantly increased rate of trapping the heavy metals.

Here, since irradiation with the cluster ions 16 is performed in thepresent invention, higher gettering capability can be achieved ascompared to cases of implanting monomer ions. Moreover, recovery heattreatment can be omitted. Therefore, the epitaxial silicon wafer 100achieving higher gettering capability can be more efficiently produced,and white spot defects are expected to be reduced more than conventionalin back-illuminated solid-state image sensing devices produced from theepitaxial silicon wafer 100 obtained by the producing methods. Note that“cluster ions” herein mean clusters formed by aggregation of a pluralityof atoms or molecules, which are ionized by being positively ornegatively charged. A cluster is a bulk aggregate having a plurality(typically about 2 to 2000) of atoms or molecules bound together.

The inventor of the present invention considers the operation achievingsuch an effect as follows.

For example, when carbon monomer ions are implanted into a siliconwafer, the monomer ions sputter silicon atoms forming the silicon waferto be implanted to a predetermined depth position in the silicon wafer,as shown in FIG. 4B. The implantation depth depends on the kind of theconstituent element of the implantation ions and the accelerationvoltage of the ions. In this case, the concentration profile of carbonin the depth direction of the silicon wafer is relatively broad, and thecarbon implanted region extends approximately 0.5 μm to 1 μm. When aplurality of species of ions are simultaneously implanted at the sameenergy, lighter elements are implanted more deeply, in other words,elements are implanted at different positions depending on their masses.Accordingly, the concentration profile of the implanted elements isbroader in such a case.

Monomer ions are typically implanted at an acceleration voltage of about150 keV to 2000 keV. However, the ions collide with silicon atoms withthe energy, which results in disrupted crystallinity of the surfaceportion of the silicon wafer, to which the monomer ions are implanted.Accordingly, the crystallinity of an epitaxial layer to be grown lateron the wafer surface is disrupted. Further, the higher the accelerationvoltage is, the more the crystallinity is disrupted. Therefore, it isrequired to perform heat treatment for recovering the crystallinityhaving been disrupted at a high temperature for a long time after ionimplantation (recovery heat treatment).

On the other hand, when cluster ions 16 formed from, for example, asilicon wafer is irradiated with carbon and boron as shown in FIG. 4A,the cluster ions 16 are instantaneously turned into a high temperaturestate of about 1350° C. to 1400° C. due to the irradiation energy, thusmelting silicon. After that, the silicon is rapidly cooled to form solidsolutions of carbon and boron in the vicinity of the surface of thesilicon wafer. Accordingly, a “modifying layer” herein means a layer inwhich the constituent element of the ions used for irradiation forms asolid solution at crystal interstitial positions or substitutionpositions in the crystal lattice of the surface portion of the siliconwafer. The concentration profile of carbon and boron in the depthdirection of the silicon wafer is sharper as compared with the case ofmonomer ions, although depending on the acceleration voltage and thecluster size of the cluster ions 16. The thickness of the region locallyirradiated with carbon and boron (that is, the modification layer) isabout 500 nm or less (for example, about 50 nm to 400 nm). Afterirradiation in the form of cluster ions, the elements are thermallydiffused to some extent in the process of forming the epitaxial layer20. Accordingly, in the concentration profile of carbon and boron afterthe formation of the epitaxial layer 20, broad diffusion regions areprovided on both sides of the peak where these elements are localized.However, the thickness of the modifying layer does not vary greatly (seeFIG. 7A described below). Consequently, carbon and boron areprecipitated at a high concentration in a localized region. Since themodifying layer 18 is formed in the vicinity of the surface of thesilicon wafer, further proximity gettering can be performed. This isconsidered to result in achievement of still higher getteringcapability. The irradiation can be performed simultaneously with aplurality of species of ions in the form of cluster ions.

In general, irradiation with cluster ions is performed at anacceleration voltage of about 10 keV/Cluster to 100 keV/Cluster.However, since a cluster is an aggregate of a plurality of atoms ormolecules, the irradiation with the ions can be performed at reducedenergy per one atom or one molecule, which reduces damage to thecrystals in the silicon wafer 10. Further, cluster ion irradiation doesnot disrupt the crystallinity of a silicon wafer 10 as compared withmonomer-ion implantation also due to the above described implantationmechanism. Accordingly, after the cluster ion irradiation step, withoutperforming recovery heat treatment on the silicon wafer 10, the siliconwafer 10 can be transferred into an epitaxial growth apparatus to besubjected to the epitaxial layer formation step.

The cluster ions 16 may include a variety of clusters depending on thebinding mode, and can be generated, for example, by known methodsdescribed in the following documents. Methods of generating gas clusterbeam are described in (1) JP 09-041138 A and (2) JP 04-354865 A. Methodsof generating ion beam are described in (1) Junzo Ishikawa, “Chargedparticle beam engineering,” ISBN 978-4-339-00734-3 CORONA PUBLISHING,(2) The Institution of Electrical Engineers of Japan, “Electron/Ion BeamEngineering,” Ohmsha, ISBN 4-88686-217-9, and (3) “Cluster IonBeam—Basic and Applications,” THE NIKKAN KOGYO SHIMBUN, ISBN4-526-05765-7. In general, a Nielsen ion source or a Kaufman ion sourceis used for generating positively charged cluster ions, whereas a highcurrent negative ion source using volume production is used forgenerating negatively charged cluster ions.

The conditions for irradiation with cluster ions 16 will be describedbelow. First, examples of the element used for irradiation include, butnot limited to, carbon, boron, phosphorus, and arsenic. In terms ofachieving higher gettering capability, the cluster ions 16 preferablycontain carbon as a constituent element. Carbon atoms at a lattice sitehave a smaller covalent radius than a single crystal silicon ingot, sothat a compression site is produced in the silicon crystal lattice,which results in high gettering capability for attracting impurities inthe lattice.

Further, the cluster ions preferably contain at least two kinds ofelements including carbon as constituent elements. Since the kinds ofmetals to be efficiently gettered depend on the kinds of theprecipitated elements, solid solutions of two or more kinds of elementscan cover a wider variety of metal contaminations. For example, carboncan efficiently getter nickel, copper, and the like, whereas boron canefficiently getter copper and iron.

The compounds to be ionized are not limited in particular, but examplesof compounds to be suitably ionized include ethane, methane, propane,dibenzyl (C₁₄H₁₄), and carbon dioxide (CO₂) as carbon sources, anddiborane and decaborane (B₁₀H₁₄) gas as boron sources. For example, whena mixed gas of dibenzyl and decaborane is used as a material gas, ahydrogen compound cluster in which carbon, boron, and hydrogen areaggregated can be produced. Alternatively, when cyclohexane (C₆H₁₂) isused as a material gas, cluster ions 16 formed from carbon and hydrogencan be produced. Further, as a carbon source compound, clustersC_(n)H_(m) (3≦n≦16, 3≦m≦10) generated from pyrene (C₁₆H₁₀), dibenzyl(C₁₄H₁₄), or the like is preferably used in particular. This facilitatesthe formation of small-sized cluster ions having a small diameter.

Next, the acceleration voltage and the cluster size of the cluster ions16 are controlled, thereby controlling the peak position of theconcentration profile of the constituent elements in the depth directionof the modifying layer 18. “Cluster size” herein means the number ofatoms or molecules constituting one cluster.

In the cluster ion step of the present invention, in terms of achievinghigher gettering capability, the irradiation with the cluster ions 16 ispreferably performed such that the peak of the concentration profile ofthe constituent elements in the depth direction of the modifying layer18 lies at a depth within 150 nm from the surface portion 10A of thesilicon wafer 10. Note that in this specification, “the concentrationprofile of the constituent elements in the depth direction” in the casewhere the constituent elements include at least two kinds of elements,means the profiles with respect to the respective single element but notwith respect to the total thereof

For a condition required to set the peak positions to the depth level,when C_(n)H_(m) (3≦n≦16, 3≦m≦10) is used for the cluster ions 16, theacceleration voltage per one carbon atom is higher than 0 keV/atom and50 keV/atom or lower, preferably 40 keV/atom or lower. Further, thecluster size is 2 to 100, preferably 60 or less, more preferably 50 orless.

In addition, for adjusting the acceleration voltage, two methods of (1)electrostatic field acceleration and (2) oscillating field accelerationare commonly used. The former method includes a method in which aplurality of electrodes are arranged at regular intervals, and the samevoltage is applied therebetween, thereby forming constant accelerationfields in the direction of the axes. The latter method includes a linearacceleration (linac) method in which ions are transferred along astraight line and accelerated with high-frequency waves. The clustersize can be adjusted by controlling the pressure of gas ejected from anozzle, the pressure of vacuum vessel, the voltage applied to thefilament in the ionization, and the like. The cluster size is determinedby finding the cluster number distribution by mass spectrometry usingthe oscillating quadrupole field or by time-of-flight mass spectrometry,and finding the mean value of the cluster numbers.

The cluster dose can be adjusted by controlling the ion irradiationtime. In the present invention, the dose of carbon is 1×10¹³ atoms/cm²or more and 1×10¹⁶ atoms/cm² or less. A dose of less than 1×10¹³atoms/cm² would lead to insufficient gettering capability, whereas adose exceeding 1×10¹⁶ atoms/cm² would cause great damage to theepitaxial surface. The cluster dose is preferably 1×10¹⁴ atoms/cm² ormore and 5×10¹⁵ atoms/cm² or less.

According to the present invention, as described above, it is notrequired to perform recovery heat treatment using a rapidheating/cooling apparatus or the like separate from the epitaxialapparatus, such as an RTA or an RTO. This is because the crystallinityof the silicon wafer 10 can be sufficiently recovered by hydrogen bakingperformed prior to epitaxial growth in an epitaxial apparatus forforming the epitaxial layer 20 to be described below. For typicalconditions for hydrogen baking, the epitaxial growth apparatus has ahydrogen atmosphere inside and the silicon wafer 10 is introduced intothe furnace at a furnace temperature of 600° C. to 900° C. and it isheated to a temperature in the range of about 1100° C. to 1200° C. at arate of 1° C./s to 15° C./s, and the temperature is kept for 30 s to 1min.

This hydrogen baking is conventionally performed for removing a naturaloxide film formed on a wafer surface due to the cleaning prior to thegrowth of the epitaxial layer. However, hydrogen baking under the aboveconditions can sufficiently recover the crystallinity of the siliconwafer 10.

Needless to say, the recovery heat treatment may be performed using aheating apparatus separate from the epitaxial apparatus after thecluster ion irradiation step prior to the epitaxial layer formationstep. This recovery heat treatment may be performed at 900° C. to 1200°C. for 10 s to 1 h. Here, the baking temperature is 900° C. to 1200° C.At a temperature lower than 900° C., it is difficult to achieve theeffect of recovering the crystallinity, whereas at a temperature ofhigher than 1200° C., slips would occur due to the high temperature heattreatment, which increases the heat load on the apparatus. Further, theheat processing time is 10 s to 1 h or less. It is difficult to achievethe effect of recovery in cases of less than 10 s, whereas theproductivity is deteriorated in cases of more than 1 h, which increasesthe heat load on the apparatus.

Such recovery heat treatment can be performed using, for example, arapid heating/cooling apparatus such as an RTA or an RTO, or a batchheating apparatus (vertical heating apparatus, horizontal heatingapparatus). The former apparatus is not suitable for long-timetreatment, since it performs heating by lamp illumination, and issuitable for heat treatment for within 15 min. On the other hand, thelatter can be used for simultaneously heating a multiplicity of wafersat a time, although it takes a long time to raise the temperature to apredetermined temperature. Further, the latter performs resistanceheating, which allows for long-time heat treatment. The heatingapparatus to be used may be selected as appropriate in consideration ofthe conditions for irradiation with the cluster ions 16.

A silicon epitaxial layer can be given as an example of the epitaxiallayer 20 formed on the modifying layer 18, and the silicon epitaxiallayer can be formed under typical conditions. For example, a source gassuch as dichlorosilane or trichlorosilane can be introduced into achamber using hydrogen as a carrier gas, so that the source material canbe epitaxially grown on the silicon wafer 10 by CVD at a temperature inthe range of about 1000° C. to 1200° C., although the growth temperaturevaries depending on the source gas to be used. The thickness of theepitaxial layer 20 is preferably in the range of 1 μm to 15 μm. When thethickness is less than 1 μm, the resistivity of the epitaxial layer 20would change due to outdiffusion of dopants from the silicon wafer 10,whereas a thickness exceeding 15 μm would affect the spectralsensitivity characteristics of the solid-state image sensing device. Theepitaxial layer 20 is used as a device layer for producing aback-illuminated solid-state image sensing device.

Next, a silicon wafer 100 produced according to the above methods willbe described. As shown in FIG. 1D, this epitaxial silicon wafer 100includes a silicon wafer 10; a modifying layer 18 formed from a certainelement contained as a solid solution in the silicon wafer 10, in asurface portion of the silicon wafer 10; and an epitaxial layer 20 onthe modifying layer 18. Here, the silicon wafer 10 is a silicon waferincluding COPs, and the full width half maximum of the concentrationprofile of the certain element in the depth direction of the modifyinglayer 18 is 100 nm or less. Specifically, according to the method ofproducing an epitaxial wafer, of the present invention, the elementconstituting cluster ions can be precipitated at a high concentration ina localized region as compared with monomer-ion implantation, whichresults in the full width half maximum of 100 nm or less. The lowerlimit of the full width half maximum can be set to 10 nm.

Note that “concentration profile in the depth direction” herein means aconcentration distribution in the depth direction, which is measured bysecondary ion mass spectrometry (SIMS). Meanwhile, “full width halfmaximum of the concentration profile of a certain element in the depthdirection” means a full width half maximum of the concentration profileof a certain element in an epitaxial layer measured by SIMS and if thethickness of the epitaxial layer exceeds 1 μm, the epitaxial layer ispreviously thinned to 1 μm considering the measurement precision.

Here, the maximum size of the COPs included in the silicon wafer 10 ispreferably 0.25 μm or less. Thus, an epitaxial silicon wafer 100 withless (reduced) epitaxial defects can be obtained. Note that the size ofCOPs in this specification means a size measured using an opticalprecipitate profiler (OPP) manufactured by Accent Optical TechnologiesCo., Ltd.

The certain element is not limited in particular as long as it is anelement other than silicon. However, carbon or at least two kinds ofelements containing carbon are preferable as described above.

In terms of achieving higher gettering capability, it is preferable thatthe peak of the concentration profile of the constituent element in thedepth direction of the modifying layer 18 lies at a depth within 150 nmfrom the surface of the silicon wafer 10 in the epitaxial silicon wafer100. Further, the peak concentration of the concentration profile ispreferably 1×10¹⁵ atoms/cm³ or more, more preferably in the range of1×10¹⁷ atoms/cm³ to 1×10²² atoms/cm³, and still more preferably in therange of 1×10¹⁹ atoms/cm³ to 1×10²¹ atoms/cm³.

The thickness of the modifying layer 18 in the thickness direction maybe approximately in the range of 30 nm to 400 nm.

The metal contamination of the epitaxial silicon wafer 100 of thepresent invention can be further suppressed by achieving highergettering capability than conventional.

For a method of producing a solid-state image sensing device accordingto an embodiment of the present invention, a solid-state image sensingdevice is formed on the epitaxial layer 20, located in the surfaceportion of the epitaxial wafer fabricated by any one of the aboveproducing methods or of any one of the above epitaxial silicon wafers,that is, the epitaxial silicon wafer 100. In solid-state image sensingdevices obtained by this producing method, formation of white spotdefects can be sufficiently suppressed than conventional.

Representative embodiments of the present invention have been describedabove. However, the present invention is not limited to thoseembodiments. For example, two epitaxial layers may be formed on thesilicon wafer 10.

EXAMPLES

First, single crystal silicon ingots were grown with varied residencetime in a temperature range of 1200° C. to 1000° C. (COP formationtemperature range). Specifically, single crystal silicon ingots (a) to(d) having four levels of COP formation regions, in which the residencetime of the ingots in the COP formation temperature range varies, weregrown using three levels of single crystal pulling apparatuses havingdifferent hot zone structures at a pulling speed adjusted such that thesingle crystal silicon ingots to be grown dwell in the temperature rangeof 1200° C. to 1000° C. for (a) 50 min, (b) 80 min, (c) 150 min, and (d)160 min.

Single crystal pulling apparatuses used for growing the above fourlevels of single crystal silicon ingots (a) to (d) are shown in FIGS. 5Aand 5B. A single crystal pulling apparatus 200 shown in FIG. 5Aincludes, in a chamber 51, a crucible 52 composed of a quartz crucible52 a and a graphite crucible 52 b for receiving polycrystalline siliconthat is a source material of a single crystal silicon ingot I andcarbon; a crucible rotating/elevating shaft 53 provided under thecrucible 52, for rotating the crucible 52 in the circumferentialdirection and vertically elevating the crucible 52; a heater 54 formelting the source material in the crucible 52 to form a material meltM; a seed crystal holder 56 attached to a tip of a lifting shaft 55, forholding a seed crystal S; a gas inlet 57 for introducing an inert gasinto the chamber 51 while growing the ingot I; an exhaust port 58 forevacuating the inert gas supplied into the chamber 51; a cylindricalheat shield 60 placed to surround the growing ingot I; and a coolingmember (water-cooling material) 59 placed inside the heat shield 60 tosurround the growing ingot I. The heat shield 60 shields the growingingot I against high temperature radiant heat from the material melt Min the crucible 52 and the side walls of the heater 54 and the crucible52, thereby adjusting the amount of incident light and the amount ofheat diffused in the vicinity of the crystal growth interface. Thecooling member 59 forcibly cools the growing single crystal ingot.

A single crystal pulling apparatus 300 shown in FIG. 5B is the same asthe apparatus 200 except for not having the cooling member 59 in theapparatus 200.

In addition, for the ingot (c), a single crystal pulling apparatus 400(not shown) was used, which can grow an ingot I with the temperaturegradient between the center part and of the edge part of the growingsingle crystal ingot (at its melting point to 1370° C.) being reduced byincreasing the gap between the lower end of the heat shield 60 and thematerial melt M in the apparatus 300.

A method of growing a single crystal silicon ingot I is described takinga case of using the above apparatus 200, for example. First, a solidmaterial such as polycrystalline silicon filling the inside of thecrucible 52 is melted by heating with the heater 54, with the chamber 51being kept in an Ar gas atmosphere under reduced pressure, therebyforming the material melt M. After that, the lifting shaft 55 is loweredto immerse the seed crystal S in the material melt M, and raising thelifting shaft 55 upward while rotating the crucible 52 and the liftingshaft 55 in a certain direction, thereby growing the ingot I downwardfrom the seed crystal S. Further, the ingot I is pulled while coolingaround the growing ingot I with the cooling member 59. When theapparatuses 300 and 400 are used, an ingot I is not cooled. Ingot growthconditions will now be described.

First, the ingot (a) was grown using the single crystal pullingapparatus 200 shown in FIG. 5A in order to shorten the residence time ofthe ingot in the temperature range of 1200° C. to 1000° C. On thatoccasion, the pulling speed was set such that the residence time of theingot I in the temperature range of 1200° C. to 1000° C. was 50 min.

Meanwhile, the ingot (b) was grown using the single crystal pullingapparatus 300 shown in FIG. 5B. The ingot (b) was grown in the samemanner as the ingot (a) except that the pulling speed was set such thatthe residence time of the ingot I in the temperature range of 1200° C.to 1000° C. was 80 min.

For the ingot (c), a single crystal pulling apparatus 400 (not shown)was used, in which the temperature gradient between the center part andof the edge part of the single crystal ingot immediately after beinggrown (at its melting point to 1370° C.) was reduced by increasing thegap between the lower end of the heat shield 60 and the material melt Min the apparatus 300 shown in FIG. 5B such that the same crystallineregion spreads in the radial direction. The growth conditions of theingot (c) were the same as those of the ingot (a) except that thepulling speed was set such that the residence time of the ingot I in thetemperature range of 1200° C. to 1000° C. was 150 min.

Further, the ingot (d) was also grown using the apparatus 300 shown inFIG. 5B as well as the ingot (b). The growth conditions of the ingot (d)were the same as those of the ingot (a) except that the pulling speedwas lower than in the case of growing the ingot (b) such that theresidence time of the ingot I in the temperature range of 1200° C. to1000° C. was 160 min.

The grown ingots (a) to (d) were n-type single crystal silicon ingotshaving a diameter of 300 mm with a crystal orientation of <100>, wherethe n-type dopant was phosphorus, and the concentration of phosphoruswas in the range of 1×10¹⁵ atoms/cm³ to 1×10¹⁷ atoms/cm³. Meanwhile, theoxygen concentration (ASTM F121-1979) was in the range of 12×10¹⁷atoms/cm³ to 14×10¹⁷ atoms/cm³.

Next, the grown four levels of single crystal silicon ingots (a) to (d)were subjected to process steps of known peripheral grinding, slicing,lapping, etching, and mirror polishing, thereby preparing silicon wafers(a) to (d) having a thickness of 725 μm.

Invention Examples 1 to 4

Subsequently, C₅H₅ clusters were generated as cluster ions using acluster ion generator (CLARIS produced by Nissin Ion Equipment Co.,Ltd.), and the silicon wafers (a) to (d) fabricated as described abovewere with the cluster ions under the conditions of dose: 1.00×10¹⁴Clusters/cm² (carbon dose: 5.00×10¹⁴ atoms/cm²), and accelerationvoltage per one carbon atom: 14.8 keV/atom. After that, each siliconwafers was transferred into a single wafer processing epitaxial growthapparatus (produced by Applied Materials, Inc.) and subjected tohydrogen baking at 1120° C. for 30 s in the apparatus. A siliconepitaxial layer (thickness: 10 μm, kind of dopant: phosphorus, dopantconcentration: 1×10¹⁵ atoms/cm³) was then epitaxially grown on thesilicon wafer by CVD at 1150° C. using hydrogen as a carrier gas andtrichlorosilane as a source gas, thereby obtaining an epitaxial siliconwafer of the present invention. Note that in Invention Examples 1 to 4,irradiation with cluster ions was performed at 80 keV/Cluster, and eachcluster was composed of five carbon atoms (atomic weight 12) and fivehydrogen atoms (atomic weight 1). Accordingly, the energy received byone carbon atom was about 14.8 keV/atom.

Comparative Examples 1 to 4

Epitaxial silicon wafers according to Comparative Examples 1 to 4 wereproduced in the same manner as in Invention Examples 1 to 3 except thatmonomer ions of carbon were produced using CO₂ as a material gas and amonomer-ion implantation step was performed under the conditions ofdose: 1.00×10¹⁴ atoms/cm² and acceleration voltage: 300 keV/atom insteadof the step of irradiation with cluster ions.

The wafers prepared in Invention Examples and Comparative Examples abovewere evaluated. The evaluation methods are shown below.

(1) SIMS Measurement

In order to explain the difference of carbon distribution betweenimmediately after irradiation with cluster ions and immediately afterimplantation of monomer ions, first, SIMS measurement was performed onthe silicon wafers of Invention Example 1 and Comparative Example 1before forming the epitaxial layers. The obtained carbon concentrationprofile is shown in FIG. 6 for reference. Here, the horizontal axis inFIG. 6 corresponds to the depth from the surface of the silicon wafer.

Next, SIMS measurement was performed on the epitaxial silicon wafers ofInvention Example 1 and Comparative Example 1. The obtained carbonconcentration profiles are shown in FIGS. 7A and 7B. The horizontal axisin each of FIGS. 7A and 7B corresponds to the depth from the surface ofthe epitaxial silicon wafer.

Further, SIMS measurement was performed on the samples prepared inInvention Examples and Comparative Examples after reducing the thicknessof the epitaxial layers to 1 μm. The full width half maximums of themeasured carbon concentration profiles are shown in Table 1. Note thatas described above, the full width half maximums shown in Table 1 areones measured by SIMS measurement after reducing the thickness of theepitaxial layers to 1 μm, so that the full width half maximums shown inTable 1 are different from those shown in FIGS. 7A and 7B. Further, thepeak position of the concentration and the peak concentration at thetime of the SIMS measurement on each sample with the thinned epitaxialwafer are also shown in Table 1.

While illustrative embodiments have been illustrated and described, itwill be appreciated that various changes can be made therein withoutdeparting from the spirit and scope of the invention.

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows:
 1. A semiconductorepitaxial wafer comprising: a silicon wafer including COPs; a modifyinglayer formed from a certain element in the silicon wafer, in a surfaceportion of the silicon wafer; and an epitaxial layer on the modifyinglayer, wherein the full width half maximum of a concentration profile ofthe certain element in the depth direction of the modifying layer is 100nm or less.
 2. The semiconductor epitaxial wafer according to claim 1,wherein the maximum size of the COPs is 0.25 μm or less.
 3. Theepitaxial silicon wafer according to claim 1, wherein the peak of theconcentration profile in the modifying layer lies at a depth within 150nm from the surface of the silicon wafer.
 4. The epitaxial silicon waferaccording to claim 1, wherein the peak concentration of theconcentration profile of the modifying layer is 1×10¹⁵ atoms/cm³ ormore.
 5. The epitaxial silicon wafer according to claim 1, wherein thecertain element includes carbon.
 6. The epitaxial silicon waferaccording to claim 5, wherein the certain element includes at least twokinds of elements including carbon.